KR20180133016A - Nanocomposite body, method for manufacturing same and nanocomposite film comprising same - Google Patents

Abstract

The present invention relates to a nanocomposite which improves compatibility with a matrix, a preparing method thereof, and a nanocomposite film using the same. The nanocomposite of the present invention comprises: an inorganic particle; a polymer matrix; and a grafting polymer chain including a polyol structure.

Description

TECHNICAL FIELD The present invention relates to a nanocomposite, a nanocomposite, a method for producing the nanocomposite, a nanocomposite film using the nanocomposite,

Nanocomposite, a method for producing the same, and a nanocomposite film using the same.

Plastic films are very thin and unbreakable and have a high degree of freedom in design, which is very useful in the field of electronic devices, in particular, in the field of flexible or stretchable displays. However, the plastic film has a disadvantage in that mechanical properties are low because the polymer is the main material.

In order to improve the mechanical properties of a plastic film, that is, a polymer film, a method of introducing inorganic particles into a polymer matrix is generally used in the production of a polymer film. However, there is a problem that aggregation occurs between particles due to the hydrophilic group on the surface of the inorganic particles. In order to solve this problem, there is a technique of introducing inorganic particles modified with hydrophobicity into a polymer matrix or treating the surface of inorganic particles with a substance having compatibility with a matrix and introducing the particles into a polymer matrix. However, Or when the introduction amount of the surface-treated inorganic particles increases, coagulation between particles still occurs.

A nanocomposite, a method for producing the same, and a nanocomposite film using the nanocomposite.

According to one aspect, inorganic particles;

Polymer matrix; And

A grafting polymer chain including a polyol structure,

Wherein the inorganic particles and the polymer matrix are connected to the grafting polymer chain.

According to another aspect, there is provided a method for preparing a hybrid nanoparticle (HNP), comprising: a first step of reacting an inorganic particle with a grafting polymer compound represented by the following formula (2) to form a hybrid nanoparticle (HNP); And

And a second step of reacting the hybrid nanoparticles with a polymer matrix.

According to another aspect, there is provided a nanocomposite film comprising the nanocomposite.

The nanocomposite includes inorganic particles, and the mechanical properties of the polymer matrix are improved, so that the grafting polymer chain is linked to the inorganic particles and the polymer matrix to improve the compatibility with the matrix. Further, by controlling the length of the grafting polymer chains Compatibility is easy to control.

Figure 1 shows the FT-IR spectrum of a PEG compound synthesized according to one embodiment.
Figure 2 shows the ¹ H-NMR spectrum of the PEG compound was synthesized according to Example ¹ H-NMR spectrum, and one embodiment of the PEGMA.
Figure 3 shows the FT-IR spectrum of the hybrid nanoparticles synthesized according to one embodiment.
4 and 5 are enlarged views of a part of the FT-IR spectrum of FIG. 3, respectively.
FIGS. 6 and 7 show ¹³ C-NMR spectra and ²⁹ Si-NMR spectra of the hybrid nanoparticles synthesized according to one embodiment, respectively.
FIG. 8 is a thermogravimetric analysis (TGA) result of the PEG compound synthesized according to an embodiment and the hybrid nanoparticles.
FIG. 9 shows the results of measurement of the size of the hybrid nanoparticles synthesized according to one embodiment in the organic solvent and the size of the fume silica nanoparticles not reacted with the PEG compound in the organic solvent.
10 is a photograph of a nanocomposite film produced according to an embodiment and a conventional nanocomposite film.
FIG. 11 shows the results of measurement of Shore hardness and elastic modulus of a nanocomposite film and a conventional film manufactured according to one embodiment.

The nanocomposite according to one embodiment comprises inorganic particles;

Polymer matrix; And

A grafting polymer chain including a polyol structure,

The inorganic particles and the polymer matrix are connected to the grafting polymer chains.

According to one embodiment, the inorganic particles and the polymer matrix are "connected" with the grafting polymer chain, meaning that any of the atoms in the grafting polymer chain is chemically bonded to any atom in the inorganic particles, May mean that other atoms in the firing chain are chemically bonded to any atom in the polymer matrix.

According to one embodiment, the inorganic particles include silica (SiO ₂₎ particles, titania (TiO ₂₎ particles, zinc oxide (ZnO ₂₎ particles, zirconia (ZrO ₂₎ particles, alumina (Al ₂ O ₃₎ particles, graphene graphene or carbon nanotube (CNT).

For example, the inorganic particles may be silica (SiO ₂ ) particles, but are not limited thereto.

According to one embodiment, the average particle size of the inorganic particles may be between 1 nm and 100 μm, for example between 10 nm and 1 μm.

The inorganic particles are connected to the polymer matrix through the grafting polymer chain and are three-dimensionally dispersed in the polymer matrix. The inorganic particles may improve mechanical properties such as strength and elasticity of the polymer matrix .

According to one embodiment, the content of the inorganic particles per 100 parts by weight of the polymer matrix may be 10 parts by weight to 50 parts by weight. When the content of the inorganic particles in the polymer matrix is 50 parts by weight or less, the inorganic particles can be evenly distributed in the polymer matrix, and when the amount is 10 parts by weight or more, the mechanical properties are enhanced.

According to one embodiment, the polymer matrix is selected from the group consisting of polyurethanes, polyesters, polyamides, epoxy resins, polycarbonates, polyethylene terephthalate. Polyethylene oxide, polyether, or any combination thereof. For example, the polymer matrix may include, but is not limited to, polyurethane.

As used herein, the term "polyol" refers to a repeating unit of a polymer, and includes, for example, polyether, polyester and the like.

According to one embodiment, the grafting polymer chain may be represented by the following formula:

≪ Formula 1 >

In Formula 1, A ₁ is -O- or -C (= O) O-.

In Formula 1, X ₁ and X ₂ independently represent a single bond, -C (= O) -, -O- , C 1 -C 20 alkylene group, C ₃ -C ₁₀ cycloalkylene group, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C _A C ₂ -C ₁₀ heterocycloalkenylene group, a C ₆ -C ₂₀ arylene group and a C ₂ -C ₂₀ heteroarylene group; And

Heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazine tank group, a C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C ₂ -C ₁₀ hetero cycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₂ - C ₂₀ heteroaryl groups substituted with at least one selected from, C ₁ -C ₂₀ alkylene group, C ₃ -C ₁₀ cycloalkylene group, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C _A C ₂ -C ₁₀ heterocycloalkenylene group, a C ₆ -C ₂₀ arylene group and a C ₂ -C ₂₀ heteroarylene group; ≪ / RTI >

According to one embodiment, X ₁ and X ₂ are independently of each other a single bond, -C (= O) -, -O- and C ₁ -C ₂₀ alkylene groups; And

A hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazino group, a C ₁ -C ₂₀ alkyl group and a C ₁ -C ₂₀ A C ₁ -C ₂₀ alkylene group substituted with at least one selected from an alkoxy group; ≪ / RTI >

For example, X ₁ and X ₂ may be independently selected from -C (═O) - and -O-, but are not limited thereto.

In the formula 1, y1 is an integer from 1 to 5, wherein y1 structure of X ₁ to not less than 2 may be the same or different from each other.

In the formula 1, y2 is an integer from 1 to 5, when the two or more y2 structure of X ₂ may be the same or different from each other.

Wherein R ₁ to R ₄ independently represent hydrogen, deuterium, a C ₁ -C ₂₀ alkyl group, a C ₂ -C ₂₀ alkenyl group, a C ₂ -C ₂₀ alkynyl group, a C ₁ -C ₂₀ alkoxy group, And

A hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazino group, a C ₁ -C ₂₀ alkyl group and a C ₁ -C ₂₀ alkoxy group may be selected from at least one substituted, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy groups selected from.

M1 is an integer of 1 to 10, and when m1 is 2 or more, the structures in parentheses are the same or different from each other,

In the above formula (1), n1 is an integer of 1 to 1,000, and when n1 is 2 or more, the structures in parentheses may be the same or different from each other.

According to one embodiment, n1 may be an integer from 50 to 500.

In the above formula (1), * denotes a binding site with an inorganic particle, and * denotes a binding site with a polymer matrix.

According to one embodiment, the grafting polymer chain may be, but is not limited to, polyethylene glycol (PEG), polylactic acid (PLA), or polycaprolactone (PCL).

According to an embodiment of the present invention, there is provided a method of preparing a nanocomposite, comprising: a first step of reacting an inorganic particle with a grafting polymer represented by Formula 2 to form hybrid nanoparticles; And

And a second step of reacting the hybrid nanoparticles with the polymer matrix:

(2)

In Formula 2, A ₁ is -O- or -C (= O) O-,

In Formula 2, R ₁ to R ₄ independently represent hydrogen, deuterium, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy; And

A hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazino group, a C ₁ -C ₂₀ alkyl group and a C ₁ -C ₂₀ alkoxy group is selected from at least one substituted, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group selected from,

M1 is an integer of 1 to 10,

In the general formula (2), n1 is an integer of 1 to 1000,

In the general formula (2), Z ₁ is a substituent which reacts with the inorganic particles.

According to one embodiment, Z ₁ is -O (Q ₁ ), -S (Q ₁ ), -Si (Q ₁ ) (Q ₂ ) (Q ₃ )

Wherein Q ₁ , Q ₂ and Q ₃ independently represent hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, , A C ₁ -C ₆₀ alkyl group, a C ₂ -C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group, a C ₁ -C ₆₀ alkoxy group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₁₀ heterocycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heteroaryl cycloalkenyl group, C ₆ -C ₆₀ aryl group, a C ₁ -C ₆₀ heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic heterocyclic A condensed polycyclic group, a biphenyl group, and a terphenyl group.

For example, Z ₁ is -Si (Q ₁₁ ) (Q ₁₂ ) (Q ₁₃ )

Wherein Q _11, Q ₁₂ and Q ₁₃ are independently C _{1- 20} alkyl group or a C _{1- 20} alkoxy date can each other, but not limited.

As another example, Z ₁ may be -OH, -Si (OC ₂ H ₅ ) ₃ , or an epoxy group.

In Formula 2, Z ₂ is a substituent that reacts with the polymer matrix.

In one embodiment, the Z ₂ is _{-O (Q 21), -S (} Q 21), -N (Q 21) (Q 22), -Si (Q 21) (Q 22) (Q 23), An isocyanate group, a carbonate group or an epoxy group,

Q ₂₁ , Q ₂₂ and Q ₂₃ are independently selected from the group consisting of hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group , A C ₁ -C ₆₀ alkyl group, a C ₂ -C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group, a C ₁ -C ₆₀ alkoxy group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₁₀ heterocycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heteroaryl cycloalkenyl group, C ₆ -C ₆₀ aryl group, a C ₁ -C ₆₀ heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic heterocyclic A condensed polycyclic group, a biphenyl group, and a terphenyl group.

For example, Z ₁ is -Si (Q ₃₁ ) (Q ₃₂ ) (Q ₃₃ )

Wherein Q _31, Q ₃₂ and Q ₃₃ are independently C _{1- 20} alkyl group or a C _{1- 20} alkoxy date can each other, but not limited.

In another example, Z ₂ may be -OH, -Si (OH) ₃ or an epoxy group, but is not limited thereto.

According to one embodiment, the inorganic particles include silica (SiO ₂₎ particles, titania (TiO ₂₎ particles, zinc oxide (ZnO ₂₎ particles, zirconia (ZrO ₂₎ particles, alumina (Al ₂ O ₃₎ particles, graphene graphene or carbon nanotube (CNT).

According to one embodiment, the inorganic particles include a first functional group on the surface, the first functional group includes at least one selected from a silanol group, a hydroxyl group and an alkoxy group, Can react with Z _{1 in the} above formula (2).

For example, the inorganic particles may be silica particles, and the inorganic particles may include a silanol group on the surface thereof, and the silanol group may react with Z _{1 in} Formula 2, but not limited thereto.

For example, the silanol group contained in the surface of the inorganic particles may react with Z _{1 in} the formula (2), and Z ₁ may be -Si (OC ₂ H ₅ ) ₃ .

In addition, the above description of the inorganic particles can be applied to the inorganic particles used in the method for producing the nanocomposite.

According to one embodiment, the grafting polymer compound represented by Formula 2 may be contained in an amount of 1 to 1000 parts by weight per 100 parts by weight of the inorganic particles. When the content of the grafting polymer compound satisfies the above range, grafting of the grafting polymer compound to the inorganic particles can be more effectively performed.

According to one embodiment, the reaction of the inorganic particles and the grafting polymer represented by Formula 2 in the first step may be a sol-gel reaction.

According to another embodiment, the inorganic particles in the first step and the grafting polymer compound represented by the following formula (2) may be reacted under a platinum catalyst. The platinum catalyst may be, for example, H ₂ PtCl ₆ , PtO ₂ , Pt (dvs), Pt (dcp), and the like.

The reaction of the first step may proceed through two reaction paths, for example, C-silylation and O-silylation as shown in Reaction Scheme 1 below.

<Reaction Scheme 1>

According to one embodiment, the C-silylation reaction can proceed in the two reaction paths shown in Reaction Scheme 1 by forming an optional structure as described below by using the platinum catalyst.

However, the description of the reaction path described above is intended to assist the understanding of the invention, and the scope of the present invention is not limited by theory.

According to one embodiment, the polymer matrix is selected from the group consisting of polyurethanes, polyesters, polyamides, epoxy resins, polycarbonates, polyethylene terephthalate. Polyethylene oxide, polyether, or any combination thereof.

According to one embodiment, the polymer matrix comprises a second functional group, and the second functional group comprises at least one selected from an isocyanate group, an epoxy group, a hydroxyl group, an amine group and a carbonate group, 2 is a functional group that can react with Z ₂ of the formula (2).

For example, the polymer matrix is polyurethane, the polymer matrix comprises an isocyanate group, and the isocyanate group may react with Z _{2 in} Formula 2, but is not limited thereto.

For example, the isocyanate group contained in the polymer matrix may react with Z _{2 in} Formula 2, and Z ₂ may be -OH.

According to one embodiment, the content of the hybrid nanoparticles per 100 parts by weight of the polymer matrix may be 10 parts by weight to 50 parts by weight. When the content of the hybrid nanoparticles in the polymer matrix is 50 parts by weight or less, the hybrid nanoparticles can be uniformly distributed in the polymer matrix, and when the hybrid nanoparticles are 10 parts by weight or more, the mechanical properties are enhanced

According to one embodiment, there is provided a nanocomposite film comprising the nanocomposite.

According to one embodiment, the Shore D hardness of the nanocomposite film may be 30 D to 60 D, for example 32 D to 42 D.

According to another embodiment, the Shore A hardness of the nanocomposite film can be 80 D to 120 D, for example 82 D to 102 D.

According to one embodiment, the modulus of elasticity of the nanocomposite film can be from 30 MPa to 100 MPa, for example from 35 MPa to 30 MPa.

In the present specification, the C ₁ -C ₆₀ alkyl group means a linear or branched aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl A tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, and the like. In the present specification, a C ₁ -C ₆₀ alkylene group means a divalent group having the same structure as the above C ₁ -C ₆₀ alkyl group.

In the present specification, the C ₂ -C ₆₀ alkenyl group means a hydrocarbon group having at least one carbon double bond at the middle or end of the C ₂ -C ₆₀ alkyl group, and specific examples thereof include an ethenyl group, a propenyl group, a butenyl group And the like. In the present specification, the C ₂ -C ₆₀ alkenylene group means a divalent group having the same structure as the C ₂ -C ₆₀ alkenyl group.

In the present specification, a C ₂ -C ₆₀ alkynyl group means a hydrocarbon group containing at least one carbon-carbon triple bond at the middle or end of the C ₂ -C ₆₀ alkyl group, and specific examples thereof include an ethynyl group, a propynyl group, . In the present specification, the C ₂ -C ₆₀ alkynylene group means a divalent group having the same structure as the C ₂ -C ₆₀ alkynyl group.

The C ₁ -C ₆₀ alkoxy group in the present specification means a monovalent group having the formula: -OA ₁₀₁ (wherein A ₁₀₁ is the above C ₁ -C ₆₀ alkyl group), and specific examples thereof include methoxy group, ethoxy group , Isopropyloxy group, and the like.

In the present specification, the C ₃ -C ₁₀ cycloalkyl group means a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclo Heptyl group and the like. The C ₃ -C ₁₀ cycloalkylene group of the specification and the second having the same structure as the above C ₃ -C ₁₀ cycloalkyl group means a group.

In the present specification, the C ₁ -C ₁₀ heterocycloalkyl group means a monovalent monocyclic group having 1 to 10 carbon atoms including at least one heteroatom selected from N, O, Si, P and S as a ring-forming atom Specific examples thereof include 1,2,3,4-oxatriazolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, and the like. In the present specification, a C ₁ -C ₁₀ heterocycloalkylene group means a divalent group having the same structure as the above-mentioned C ₁ -C ₁₀ heterocycloalkyl group.

In the present specification, the C ₃ -C ₁₀ cycloalkenyl group is a monovalent monocyclic group having 3 to 10 carbon atoms, which has at least one double bond in the ring, but does not have an aromaticity, Examples include a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group and the like. In the present specification, the C ₃ -C ₁₀ cycloalkenylene group means a divalent group having the same structure as the C ₃ -C ₁₀ cycloalkenyl group.

In the present specification, the C ₁ -C ₁₀ heterocycloalkenyl group is a monovalent monocyclic group having 1 to 10 carbon atoms including at least one hetero atom selected from N, O, Si, P and S as a ring-forming atom, Lt; RTI ID = 0.0 &gt; a &lt; / RTI &gt; Specific examples of the C ₁ -C ₁₀ heterocycloalkenyl group include 4,5-dihydro-1,2,3,4-oxatriazolyl, 2,3-dihydrofuranyl, 2,3-dihydro A thiophenyl group and the like. In the present specification, the C ₁ -C ₁₀ heterocycloalkenylene group means a divalent group having the same structure as the C ₁ -C ₁₀ heterocycloalkenyl group.

In the present specification, the C ₆ -C ₆₀ aryl group means a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the C ₆ -C ₆₀ arylene group means a carbocyclic aromatic system having 6 to 60 carbon atoms Quot; refers to a divalent group having &lt; RTI ID = 0.0 &gt; Specific examples of the C ₆ -C ₆₀ aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, a cryanecyl group and the like. The C ₆ -C ₆₀ aryl groups and C ₆ -C ₆₀ arylene If the group contains two or more rings, the 2 or more rings may be fused to each other.

As used herein, a C ₁ -C ₆₀ heteroaryl group is a monovalent group having at least one heteroatom selected from N, O, Si, P and S as a ring-forming atom and having a heterocyclic aromatic system having 1 to 60 carbon atoms , Wherein the C ₁ -C ₆₀ heteroarylene group is optionally substituted with one or more substituents selected from the group consisting of 2 having a heterocyclic aromatic system containing from 1 to 60 carbon atoms and at least one heteroatom selected from N, O, Si, P and S as ring- Means a group. Specific examples of the C ₁ -C ₆₀ heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group and the like. When the C ₁ -C ₆₀ heteroaryl group and the C ₁ -C ₆₀ heteroarylene group include two or more rings, two or more rings may be condensed with each other.

In the present specification, the C ₆ -C ₆₀ aryloxy group indicates -OA ₁₀₂ (wherein A ₁₀₂ is the C ₆ -C ₆₀ aryl group), the C ₆ -C ₆₀ arylthio is -SA ₁₀₃ , And A ₁₀₃ is the above-mentioned C ₆ -C ₆₀ aryl device).

In the present specification, a monovalent non-aromatic condensed polycyclic group is a condensed polycyclic group in which two or more rings are condensed with each other and contain only carbon as a ring-forming atom, and the whole molecule is a non-aromaticity. (E. G., Having from 8 to 60 carbon atoms). Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group and the like. In the present specification, the divalent non-aromatic condensed polycyclic group means a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group.

In the present specification, a monovalent non-aromatic condensed heteropolycyclic group is a monovalent aromatic condensed heteropolycyclic group in which two or more rings are condensed with each other and at least one of N, O, Si, P and S Means a monovalent group (for example, having from 1 to 60 carbon atoms) having a hetero atom and having a non-aromatic group as a whole molecule. Specific examples of the monovalent non-aromatic heterocyclic polycyclic group include a carbazolyl group and the like. In the present specification, the divalent non-aromatic heterocyclic polycyclic group means a divalent group having the same structure as the monovalent non-aromatic heterocyclic polycyclic group.

The following examples illustrate the invention without limiting the scope of the invention.

[Example]

Example  One: hybrid  Manufacture of nanoparticles

One) Grafting  Synthesis of polymer compounds

Triethoxysilane and polyethylene glycol methacrylate (PEGMA, 500 g / mol) were dissolved in anhydrous toluene at a molar ratio of 1: 1 to prepare a mixed solution. 0.2 ml of Karstedt's catalyst [PT (dvs), 2 wt% in xylene] was added to the mixture, and the mixture was stirred at room temperature for 30 minutes and then heated to 80 ° C for hydrosilylation for 12 hours.

After completion of the reaction, the catalyst was adsorbed using activated carbon at room temperature for 2 hours and filtered using a column made of silica gel and celite. The solvent was removed by reducing the pressure at 60 DEG C for 8 hours to obtain a grafting polymer compound PEG compound. The structure of the PEG compound was confirmed by FT-IR spectroscopy and ¹ H-NMR spectroscopy.

The FT-IR spectrum of the synthesized PEG compound is shown in FIG. Also, it exhibited ¹ H-NMR spectrum of ¹ H-NMR spectrum of the reaction is PEGMA, and the synthesized PEG compound to Figure 2.

2) hybrid  Synthesis of nanoparticles

Fumed silica nanoparticles (particle size 7 nm, 6 g, Sigma-Aldrich) were dissolved in 100 ml of a mixed solvent of tetrahydrofuran (THF, Sigma-Aldrich) and distilled water (v / v = 3: Lt; / RTI &gt; and dispersed evenly.

18 g of the synthesized PEG compound was hydrolyzed in advance using a 2N hydrochloric acid aqueous solution and then introduced into a dispersion solvent of fumed silica nanoparticles. The mixture was stirred at 80 DEG C for 18 hours to effect a sol-gel reaction. The precipitate formed by introducing excess amount of diethyl ether as a low-solubility solvent was filtered and dried at 80 DEG C for 1 hour.

The dried precipitate was washed again with toluene and ethanol to remove residual PEG, and then dried at 80 DEG C for 12 hours to obtain hybrid nanoparticles.

Example  2: hybrid  Confirmation of synthesis of nanoparticles

The structure of the hybrid nanoparticles was confirmed by FT-IR spectroscopy and NMR spectroscopy.

The FT-IR spectrum of the synthesized hybrid nanoparticles is shown in FIG. Some of the FT-IR spectrum of FIG. 3 is enlarged and shown in FIG. 4 and FIG.

The ¹³ C-NMR spectrum and the ²⁹ Si-NMR spectrum of the synthesized hybrid nanoparticles are shown in FIGS. 6 and 7, respectively.

Referring to FIG. 6, it was confirmed that the structure of the PEG compound was also maintained in the hybrid nanoparticles. 7, a structure represented by "T" was formed, and it was confirmed that a chemical bond was formed due to a sol-gel reaction between the PEG compound and the silanol group of the fumed silica nanoparticles.

Example  3: hybrid  Of nanoparticles Thermogravimetry  And Grafting  Density evaluation

The results of thermogravimetric analysis (TGA) of the synthesized PEG compound and the hybrid nanoparticles are shown in FIG. Referring to FIG. 8, the grafting density was calculated in accordance with Equation (1) below.

&Lt; Formula 1 >

The <Formula 1> of, Δ W _HNP represents weight reduction of the hybrid nanoparticles (weight loss,%), Δ W _silica represents weight reduction rate (%) of a fume silica nanoparticles, M is the molecular weight of the PEG (664.27 g / mol), and S _spec represents the surface area of fumed silica (provided by Sigma-Aldrich).

Example  4: hybrid  Particle size analysis of nanoparticles

The synthesized hybrid nanoparticles in the organic solvent and the fume silica nanoparticles not reacted with the PEG compound were analyzed for particle size using zeta potential and particle size analyzer, respectively, and the results are shown in FIG. In the particle size analysis, each suspension was introduced into ethanol in an amount of 1 wt% and ultrasonically dispersed for 5 minutes. The suspended solution was filtered using a 0.2 μm filter, and the size of each particle was measured using a zeta potential and particle size analyzer Respectively.

Referring to FIG. 9, it was confirmed that the hybrid nanoparticles have improved dispersibility in the organic solvent as compared with the conventional fumed silica nanoparticles, and are dispersed in the organic solvent as small-sized particles without aggregation.

Example  5: Preparation of nanocomposite film

The polyurethane prepolymer (PU prepolymer) and the hybrid nanoparticles were dispersed in tetrahydrofuran (THF) in an amount of 33 wt%, respectively. The introduced amount of the hybrid nanoparticles was adjusted to 10 wt%, and the mixture was stirred at room temperature for 3 hours .

The solution was coated on a release paper using a coater and then cured at 80 DEG C for 6 hours to prepare a nanocomposite film.

Example  6: Observation of properties of nanocomposite film

Physical properties of the nanocomposite film and the nanocomposite film prepared using the existing fumed silica nanoparticles instead of the hybrid nanoparticles were visually observed, and the photograph is shown in FIG.

Referring to FIG. 10, in the nanocomposite film produced using the existing fumed silica nanoparticles, the film was not formed well due to the aggregation of particles, and a crack was formed on the surface. However, the hybrid nanoparticle The nanocomposite films prepared by using the polyaniline nanoparticles showed higher compatibility and reactivity and thus were uniformly introduced into the film to produce a uniform film.

Example  7: Nano Composite Film Shore  Evaluation of hardness and modulus

Shore hardness was measured according to ASTM D2240 for a polyurethane film, a film prepared by introducing a fumed silica particle into a polyurethane, and a nanocomposite film prepared by introducing the hybrid nanoparticles into a polyurethane, and the shore hardness was measured according to ASTM D638 The elastic modulus was measured according to D882. The results are shown in Fig.

Referring to FIG. 11, it was confirmed that the nanocomposite film prepared by introducing hybrid nanoparticles into the polyurethane according to one embodiment exhibits excellent physical properties such that the hardness and the elastic modulus are improved as compared with the film using the conventional material.

Claims (20)

Inorganic particles;
Polymer matrix; And
A grafting polymer chain including a polyol structure,
Wherein the inorganic particles and the polymer matrix are connected to the grafting polymer chains. The method of claim 1, wherein the inorganic particles include silica (SiO ₂₎ particles, titania (TiO ₂₎ particles, zinc oxide (ZnO ₂₎ particles, zirconia (ZrO ₂₎ particles, alumina (Al ₂ O ₃₎ particles, graphene (graphene) or carbon nanotube (CNT). The nanocomposite according to claim 1, wherein the inorganic particles have an average particle diameter of 1 nm to 100 μm. The nanocomposite according to claim 1, wherein the content of the inorganic particles per 100 parts by weight of the polymer matrix is 10 parts by weight to 50 parts by weight. The method of claim 1, wherein the polymer matrix is selected from the group consisting of polyurethane, polyester, polyamide, epoxy resin, polycarbonate, polyethylene terephthalate. Polyethylene oxide, polyether, or any combination thereof. The grafting polymer chain according to claim 1, wherein the grafting polymer chain is represented by the following formula (1)
&Lt; Formula 1 >

In Formula 1,
A ₁ is -O- or -C (= O) O-,
X ₁ and X ₂ are, independently of each other, a single bond, -C (= O) -, -O- , C 1 -C 20 alkylene group, C ₃ -C ₁₀ cycloalkylene group, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C _A C ₂ -C ₁₀ heterocycloalkenylene group, a C ₆ -C ₂₀ arylene group and a C ₂ -C ₂₀ heteroarylene group; And
Heavy hydrogen, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazine tank group, a C ₁ -C ₂₀ alkyl, C ₁ -C ₂₀ alkoxy group, C ₃ -C ₁₀ cycloalkyl, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C ₂ -C ₁₀ hetero cycloalkenyl group, C ₆ -C ₂₀ aryl group and C ₂ - C ₂₀ heteroaryl groups substituted with at least one selected from, C ₁ -C ₂₀ alkylene group, C ₃ -C ₁₀ cycloalkylene group, C ₃ -C ₁₀ cycloalkenyl group, C ₂ -C ₁₀ heterocycloalkyl group, C _A C ₂ -C ₁₀ heterocycloalkenylene group, a C ₆ -C ₂₀ arylene group and a C ₂ -C ₂₀ heteroarylene group; &Lt; / RTI &gt;
y1 is an integer of 1 to 5,
when y1 is 2 or more, the structures of X &lt; _{1 &gt}; are the same or different from each other,
y2 is an integer of 1 to 5,
when y2 is 2 or more, the structures of X &lt; ₂ &gt; are the same or different from each other,
R ₁ to R ₄ independently represent hydrogen, deuterium, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy; And
A hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazino group, a C ₁ -C ₂₀ alkyl group and a C ₁ -C ₂₀ alkoxy group is selected from at least one substituted, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group selected from,
m1 is an integer of 1 to 10,
When m1 is 2 or more, the structures in parentheses are the same or different from each other,
n1 is an integer of 1 to 1,000,
When n1 is 2 or more, the structures in parentheses are the same or different from each other,
* Is a binding site with inorganic particles,
* 'Is a binding site with a polymer matrix. The nanocomposite according to claim 1, wherein the grafting polymer chain is polyethylene glycol (PEG), polylactic acid (PLA), or polycaprolactone (PCL). A first step of reacting an inorganic particle with a grafting polymer compound represented by the following formula 2 to form hybrid nanoparticles; And
And a second step of reacting the hybrid nanoparticles with a polymer matrix.
(2)

In Formula 2,
A ₁ is -O- or -C (= O) O-,
R ₁ to R ₄ independently represent hydrogen, deuterium, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl, C ₁ -C ₂₀ alkoxy; And
A hydroxyl group, a cyano group, an epoxy group, a nitro group, an amidino group, a hydrazino group, a hydrazino group, a C ₁ -C ₂₀ alkyl group and a C ₁ -C ₂₀ alkoxy group is selected from at least one substituted, C ₁ -C ₂₀ alkyl, C ₂ -C ₂₀ alkenyl, C ₂ -C ₂₀ alkynyl group, C ₁ -C ₂₀ alkoxy group selected from,
m1 is an integer of 1 to 10,
n1 is an integer of 1 to 1000,
Z ₁ is a substituent which reacts with the inorganic particles,
Z ₂ is a substituent that reacts with the polymer matrix. The compound according to claim 8, wherein Z ₁ is -O (Q ₁ ), -S (Q ₁ ), -Si (Q ₁ ) (Q ₂ ) (Q ₃ )
Wherein Q ₁ , Q ₂ and Q ₃ independently represent hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, , A C ₁ -C ₆₀ alkyl group, a C ₂ -C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group, a C ₁ -C ₆₀ alkoxy group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₁₀ heterocycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heteroaryl cycloalkenyl group, C ₆ -C ₆₀ aryl group, a C ₁ -C ₆₀ heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic heterocyclic A condensed polycyclic group, a biphenyl group, and a terphenyl group. The method of claim 8, wherein Z ₂ is _{-O (Q 21), -S (} Q 21), -N (Q 21) (Q 22), -Si (Q 21) (Q 22) (Q 23), An isocyanate group, a carbonate group or an epoxy group,
Q ₂₁ , Q ₂₂ and Q ₂₃ are independently selected from the group consisting of hydrogen, deuterium, -F, -Cl, -Br, -I, a hydroxyl group, a cyano group, a nitro group, an amidino group, a hydrazino group , A C ₁ -C ₆₀ alkyl group, a C ₂ -C ₆₀ alkenyl group, a C ₂ -C ₆₀ alkynyl group, a C ₁ -C ₆₀ alkoxy group, a C ₃ -C ₁₀ cycloalkyl group, a C ₁ -C ₁₀ heterocycloalkyl group, a C ₃ -C ₁₀ cycloalkenyl group, C ₁ -C ₁₀ heteroaryl cycloalkenyl group, C ₆ -C ₆₀ aryl group, a C ₁ -C ₆₀ heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic heterocyclic A condensed polycyclic group, a biphenyl group, and a terphenyl group. The inorganic particles may be selected from the group consisting of silica (SiO ₂ ) particles, titania (TiO ₂ ) particles, zinc oxide (ZnO ₂ ) particles, zirconia (ZrO ₂ ) particles, alumina (Al ₂ O ₃ ) particles, graphene, Tube &lt; / RTI &gt; (CNT). 12. The method of claim 11, wherein the inorganic particles comprise a first functional group on the surface,
The first functional group includes at least one selected from a silanol group, a hydroxyl group, and an alkoxy group,
, Nanocomposites of the first functional groups are reacted with Z ₁ of the general formula (2). The method of producing a nanocomposite according to claim 8, wherein the inorganic particles have an average particle diameter of 1 nm to 100 μm. The method of producing a nanocomposite according to claim 1, wherein the grafting polymer compound represented by Formula 2 is contained in an amount of 1 to 1000 parts by weight per 100 parts by weight of the inorganic particles. The method of claim 8, wherein the polymer matrix is selected from the group consisting of polyurethane, polyester, polyamide, epoxy resin, polycarbonate, polyethylene terephthalate. Polyethylene oxide, polyether, or any combination thereof. 16. The method of claim 15, wherein the polymer matrix comprises a second functional group,
The second functional group includes at least one selected from an isocyanate group, an epoxy group, a hydroxyl group, an amine group and a carbonate group,
The method of the second functional group is reactive with Z ₂ of Formula 2, the nanocomposite. The method of producing a nanocomposite according to claim 8, wherein the content of the hybrid nanoparticles is from 10 parts by weight to 50 parts by weight per 100 parts by weight of the polymer matrix. A nanocomposite film comprising the nanocomposite of any one of claims 1 to 7. 19. The nanocomposite film of claim 18, wherein the Shore D hardness is 30 D to 60 D. 19. The nanocomposite film of claim 18, wherein the modulus of elasticity is from 30 MPa to 100 MPa.

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